阅读说明：本技术 铝硅酸盐玻璃、强化玻璃及其制备方法、盖板、背板及装置 (Aluminosilicate glass, tempered glass, preparation methods of aluminosilicate glass and tempered glass, cover plate, back plate and device ) 是由 肖子凡 周翔磊 平文亮 刘建党 陈志鸿 戴斌 刘攀 于 2019-10-10 设计创作，主要内容包括：本发明涉及一种铝硅酸盐玻璃、强化玻璃及其制备方法、盖板、背板及装置。以质量百分含量计,该铝硅酸盐玻璃包括55％～65％的SiO<Sub>2</Sub>、13％～26％的Al<Sub>2</Sub>O<Sub>3</Sub>、2％～6％的Li<Sub>2</Sub>O、6％～11％的Na<Sub>2</Sub>O、1％～6％的K<Sub>2</Sub>O、0.1％～3％的B<Sub>2</Sub>O<Sub>3</Sub>及0.1％～4％的ZrO<Sub>2</Sub>。上述铝硅酸盐玻璃经化学强化之后具有更优异的抗粗糙地面跌落破碎性能和更好的抗力学冲击性能。(The invention relates to aluminosilicate glass, tempered glass, a preparation method of the aluminosilicate glass, a cover plate, a back plate and a device. The aluminosilicate glass comprises 55-65% of SiO by mass percentage 2 13 to 26 percent of Al 2 O 3 2 to 6 percent of Li 2 O, 6 to 11 percent of Na 2 O, 1 to 6 percent of K 2 O, 0.1-3% of B 2 O 3 And 0.1 to 4 percent of ZrO 2 . The aluminosilicate glass has more excellent anti-rough ground falling and crushing performance and better mechanical impact resistance after being chemically strengthened.)

1. The aluminosilicate glass is characterized by comprising 55-65% of SiO in percentage by mass₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃And 0.1 to 4 percent of ZrO₂。

2. The aluminosilicate glass of claim 1, wherein the SiO₂The mass percentage content of the active ingredients is 58-63 percent; and/or

The Al is₂O₃The mass percentage content of the compound is 16-24 percent; and/or

The Li₂The mass percentage of O is 3-5.5%; and/or

The Na is₂The mass percentage of O is 7-10%; and/or

Said K₂The mass percentage of O is 2.5-4%; and/or

B is₂O₃The mass percentage content of the compound is 0.1-3 percent; and/or

The ZrO₂The mass percentage of the component (A) is 0.1-4%.

3. The aluminosilicate glass of claim 2,the Al is₂O₃The mass percentage of the component (A) is 19-22%.

4. The aluminosilicate glass according to any one of claims 1 to 3, wherein the aluminosilicate glass further comprises MgO in an amount of not more than 4% by mass; and/or

The aluminosilicate glass also comprises ZnO with the content not more than 3 percent by mass; and/or

The aluminosilicate glass also comprises P with the content not more than 3 percent by mass₂O₅。

5. The aluminosilicate glass of claim 4, wherein the MgO is present in an amount of 1 to 3% by mass; and/or

The mass percentage of the ZnO is not more than 1.5 percent; and/or

The P is₂O₅The mass percentage of (A) is not more than 1%.

6. A preparation method of tempered glass is characterized by comprising the following steps:

immersing the aluminosilicate glass of any one of claims 1 to 5 in a molten salt for ion exchange to obtain a strengthened glass; wherein the molten salt comprises NaNO₃And KNO₃In the ion exchange, Li of the aluminosilicate glass⁺Na with the molten salt⁺Exchange rate of (A) and Na of the aluminosilicate glass⁺K with the molten salt⁺The ratio of the exchange rates of (A) is 4.8 to 6.3.

7. The method according to claim 6, wherein the molten salt contains 5 to 25 mass% of NaNO₃And 75 to 95 percent of KNO₃(ii) a And/or

The temperature of the ion exchange is 390-460 ℃; and/or

The time of the ion exchange is more than 180 min.

8. The method for producing a strengthened glass according to claim 6 or 7, wherein the molten salt contains 5 to 10 mass% of NaNO₃And 90% -95% KNO₃(ii) a And/or

The temperature of the ion exchange is 410-440 ℃; and/or

The time of the ion exchange is 180 min-300 min.

9. The method for producing a strengthened glass according to claim 6, wherein the method further comprises a step of removing the molten salt from the surface of the strengthened glass after the step of immersing the aluminosilicate glass according to any one of claims 1 to 5 in the molten salt to perform ion exchange to obtain the strengthened glass.

10. The method for producing a strengthened glass according to claim 6, further comprising a step of producing the aluminosilicate glass before the step of immersing the aluminosilicate glass according to any one of claims 1 to 5 in the molten salt to perform ion exchange to obtain the strengthened glass.

11. The method for producing a strengthened glass according to claim 10, wherein the step of producing the aluminosilicate glass comprises:

mixing the raw materials for preparing the silicate glass with a glass clarifier, and then carrying out melting treatment at 1600-1680 ℃ to obtain glass liquid; and

and forming the molten glass, and then annealing at 550-650 ℃ to obtain the silicate glass.

12. The method for producing a strengthened glass according to claim 6, further comprising a step of polishing the aluminosilicate glass before the step of immersing the aluminosilicate glass according to any one of claims 1 to 5 in the molten salt for ion exchange to obtain the strengthened glass.

13. The method for producing a strengthened glass according to claim 12, further comprising a step of subjecting the aluminosilicate glass to a hot bending treatment after the step of subjecting the aluminosilicate glass to a polishing treatment.

14. A tempered glass produced by the method for producing a tempered glass according to any one of claims 6 to 13.

15. A cover sheet comprising the strengthened glass of claim 14.

16. A backsheet comprising the strengthened glass of claim 14.

17. An apparatus comprising the strengthened glass of claim 14.

Technical Field

The invention relates to the field of glass manufacturing, in particular to aluminosilicate glass, tempered glass, a preparation method of the aluminosilicate glass, a cover plate, a back plate and a device.

Background

With the development of mobile internet 5G communication technology and wireless charging technology, more and more electronic products begin to use the design of double-sided glass. For example, in pursuit of the design concepts of thinness, differentiation and individuation such as narrow frames, more and more mobile phones adopt the design of a cover plate or a back plate of 3D curved glass.

When the glass produced by the traditional process is subjected to performance tests such as complete machine drop test and complete machine roller test on rough (sand paper) ground, most of the performance and data result stability is not ideal enough, and particularly, compared with the drop height and the breaking height of smooth ground, the drop breaking height of the rough ground is attenuated by more than 40%.

The method aims at the problem that most of performances and data result stability are not ideal when the glass is subjected to performance tests such as a complete machine drop test on a rough (sand paper) ground and a complete machine roller test. In recent years, two types of glass with better anti-falling performance appear. One is high alumina glass prepared by a one-step ion-exchange chemical strengthening process, and the other is glass prepared by a two-step or multi-step ion-exchange chemical strengthening process.

The high-alumina glass has high alumina content, higher strength than common soda-lime glass, and higher ion exchange capacity, is mainly applied to protective cover plates, protective paster glass and the like of electronic products, and has higher visible light transmittance. At present, the high-alumina glass is pure potassium nitrate molten salt (Na in the molten salt) at the temperature of 390 to 450 DEG C⁺Concentration controlled within 4000 ppm) for 2h to 8h, the surface Compressive Stress (CS) is generally above 650MPa, and the depth of layer (DOL) of the surface compressive stress is above 30 μm. When the ion exchange time is more than 7h, the depth of the surface compressive stress layer can be increased to about 60 mu m, but still far reachesLess than 80 μm, and the surface compressive stress value is correspondingly reduced, which easily causes the formation of an alkali-rich layer on the surface of the strengthened glass, which is difficult to remove, and further forms micro-crack defects, thus seriously affecting the overall strength of the glass.

The glass prepared by the chemical strengthening process of two-step or multi-step ion exchange mainly introduces Li in the composition of the glass₂And O, carrying out a two-step or multi-step ion exchange chemical strengthening process, and respectively finishing the ion exchange of Li-Na and Na-K by controlling the difference of the molten salt concentration in the first step and the molten salt concentration in the second step so as to obtain higher surface compressive stress layer depth and better surface compressive stress value. The glass prepared by the chemical strengthening process of two-step or multi-step ion exchange can realize that the depth of a surface compressive stress layer is more than 80 mu m, and the value of the surface compressive stress is more than 600 MPa. However, the two-step or multi-step ion exchange chemical strengthening process is difficult to control the whole process time within 5h in practical application, and the pollution problem of molten salt is easy to occur.

Disclosure of Invention

In view of the above, there is a need for a method for producing strengthened glass having high shatter resistance, which is less time-consuming and less likely to cause molten salt contamination.

In addition, the aluminosilicate glass for preparing the strengthened glass with strong anti-falling performance, the cover plate, the back plate and the device are also provided.

The aluminosilicate glass comprises 55-65% of SiO by mass percentage₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃And 0.1 to 4 percent of ZrO₂。

The glass transition temperature of the aluminosilicate glass is not lower than 515 ℃, and the surface micro Vickers hardness is not lower than 630 MPa. The aluminosilicate glass has more excellent anti-rough ground falling and crushing performance and better mechanical impact resistance after being chemically strengthened. The aluminosilicate glass satisfies the following requirements after being chemically strengthened: the depth of the surface compressive stress layer is not less than 75 mu m; the surface compressive stress value is between 650MPa and 900 MPa; the intermediate tensile stress of the aluminosilicate glass with the thickness of 0.5mm is not higher than 80 MPa; the intermediate tensile stress of the aluminosilicate glass with the thickness of 0.7mm is not higher than 60 MPa.

In one embodiment, the SiO₂The mass percentage content of the active ingredients is 58-63 percent; and/or

The Al is₂O₃The mass percentage content of the compound is 16-24 percent; and/or

The Li₂The mass percentage of O is 3-5.5%; and/or

The Na is₂The mass percentage of O is 7-10%; and/or

Said K₂The mass percentage of O is 2.5-4%; and/or

B is₂O₃The mass percentage content of the compound is 0.1-3 percent; and/or

The ZrO₂The mass percentage of the component (A) is 0.1-4%.

In one embodiment, the Al₂O₃The mass percentage of the component (A) is 19-22%.

In one embodiment, the aluminosilicate glass further comprises MgO in an amount of not more than 4% by mass; and/or

The aluminosilicate glass also comprises ZnO with the content not more than 3 percent by mass; and/or

The aluminosilicate glass also comprises P with the content not more than 3 percent by mass₂O₅。

In one embodiment, the MgO accounts for 1-3% by mass; and/or

The mass percentage of the ZnO is not more than 1.5 percent; and/or

The P is₂O₅The mass percentage of (A) is not more than 1%.

A preparation method of tempered glass comprises the following steps:

immersing the aluminosilicate glass into molten salt for ion exchangeObtaining the strengthened glass; wherein the molten salt comprises NaNO₃And KNO₃In the ion exchange, Li of the aluminosilicate glass⁺Na with the molten salt⁺Exchange rate of (A) and Na of the aluminosilicate glass⁺K with the molten salt⁺The ratio of the exchange rates of (A) is 4.8 to 6.3.

In one embodiment, the molten salt comprises 5-25% of NaNO by mass percentage₃And 75 to 95 percent of KNO₃(ii) a And/or

The temperature of the ion exchange is 390-460 ℃; and/or

The time of the ion exchange is more than 180 min.

In one embodiment, the molten salt comprises 5-10% of NaNO by mass percentage₃And 90% -95% KNO₃(ii) a And/or

The temperature of the ion exchange is 410-440 ℃; and/or

The time of the ion exchange is 180 min-300 min.

In one embodiment, after the step of immersing the aluminosilicate glass into the molten salt for ion exchange to obtain the strengthened glass, the method further comprises a step of removing the molten salt on the surface of the strengthened glass.

In one embodiment, the method further comprises a step of preparing the aluminosilicate glass before the step of immersing the aluminosilicate glass into the molten salt for ion exchange to obtain the strengthened glass.

In one embodiment, the step of preparing the aluminosilicate glass comprises:

mixing the raw materials for preparing the silicate glass with a glass clarifier, and then carrying out melting treatment at 1600-1680 ℃ to obtain glass liquid; and

and forming the molten glass, and then annealing at 550-650 ℃ to obtain the silicate glass.

In one embodiment, before the step of immersing the aluminosilicate glass in a molten salt for ion exchange to obtain a strengthened glass, the method further comprises a step of polishing the aluminosilicate glass.

In one embodiment, after the step of polishing the aluminosilicate glass, the step of subjecting the aluminosilicate glass to a hot bending process is further included.

A tempered glass is prepared by the preparation method of the tempered glass.

A cover plate comprises the tempered glass.

A back plate comprises the tempered glass.

An apparatus comprising the above strengthened glass.

Detailed Description

In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

One embodiment of the present invention provides an aluminosilicate glass which satisfies, after being chemically strengthened: the depth of the surface compressive stress layer is not less than 75 mu m; the surface compressive stress value is between 650MPa and 900 MPa; the intermediate tensile stress of the aluminosilicate glass with the thickness of 0.5mm is not higher than 80 MPa; the intermediate tensile stress of the aluminosilicate glass with the thickness of 0.7mm is not higher than 60 MPa. The aluminosilicate glass has more excellent anti-rough ground falling and crushing performance and better mechanical impact resistance after being chemically strengthened. In addition, the glass transition temperature of the aluminosilicate glass is not lower than 515 ℃, and the surface micro Vickers hardness is not lower than 630 HV.

Specifically, the above aluminosilicate is contained in mass percentageThe glass comprises 55 to 65 percent of SiO₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃And 0.1 to 4 percent of ZrO₂。

Silicon dioxide (SiO)₂) Is an essential component for forming the skeleton of aluminosilicate glass. SiO 2₂The strength and chemical stability of the aluminosilicate glass can be improved; SiO 2₂Higher strain points and lower coefficients of thermal expansion can be achieved for aluminosilicate glasses. SiO 2₂The mass percentage of the component (A) is 55-65%. When SiO is present₂When the mass percentage of (b) is less than 55%, the formed aluminosilicate glass has a poor main network structure, poor mechanical properties and poor weather resistance. When SiO is present₂When the mass percentage of the aluminum silicate glass is over 65 percent, the melting temperature in the production process of the aluminum silicate glass is correspondingly increased, so that the energy consumption is correspondingly increased, and the defects of frequent bubbles, stones and the like are easily caused; and, due to SiO₂The content of the silica-alumina composite is more than 65 percent by mass, the proportion of the silica skeleton structure is higher, and the network gap is smaller, so that the silica-alumina composite is not beneficial to ion exchange in a chemical strengthening process and influences the efficiency of chemical strengthening. Further, SiO₂The mass percentage of the component (A) is 58-63%.

Alumina (Al)₂O₃) Is an essential component for increasing the ion exchange capacity of aluminosilicate glass, and at the same time, it can improve the chemical stability of the glass. Due to Al₂O₃The volume of the network space formed by the prepared aluminosilicate glass can be different according to the content. Al (Al)₂O₃The higher the content is, the larger the gap of the framework network of the aluminosilicate glass is, and the more favorable the ion exchange is; however, the thermal expansion coefficient of aluminosilicate glass is not caused by Al₂O₃The content is further reduced due to overhigh content, but the high-temperature viscosity of the aluminosilicate glass is obviously increased, the melting temperature is correspondingly increased, the energy consumption is correspondingly increased, and the defects of bubbles, stones and the like are easy to appear. However, when Al of the aluminosilicate glass is present₂O₃At a low content, aluminosilicate glassThe network space of the glass has smaller gaps, which is not beneficial to ion migration and influences the efficiency of chemical strengthening. Thus, Al₂O₃The mass percentage of the component (A) is 13-26%. Further, Al₂O₃The mass percentage of the component (A) is 16-24%. Further, Al₂O₃The mass percentage of the component (A) is 19-22%.

Lithium oxide (Li)₂O) is a flux, and is an essential component for the chemical strengthening process for producing strengthened glass in the present embodiment. Due to Li⁺The high-temperature viscosity can be effectively reduced at high temperature due to the polarization characteristic of the high-temperature-resistant epoxy resin. The molten salt used in the chemical strengthening process for producing strengthened glass according to the embodiment includes NaNO₃And KNO₃. By Li in aluminosilicate glass⁺With Na in the molten salt⁺By ion exchange, the depth of the surface compressive stress layer can be increased in a short time, so that the glass has more excellent mechanical impact resistance. Li₂The mass percentage of O is 2-6%. When Li is present₂When the mass percentage of O is less than 2%, the aluminosilicate glass is difficult to obtain higher surface compressive stress depth of layer; when Li is present₂When the mass percentage of O is higher than 6%, the manufacturing cost is increased, the glass expansion coefficient is remarkably increased, the glass crystallization tendency is too high, and the probability of generating stone defects is remarkably increased. Further, Li₂The mass percentage of O is 3-5.5%.

Sodium oxide (Na)₂O) is another fluxing agent that significantly lowers the melting temperature of aluminosilicate glasses and is also an essential component for ion exchange. Na (Na)₂The mass percentage of O is 6-11%. When the mass percentage is less than 6%, not only the melting performance of the aluminosilicate glass is deteriorated, but also the stress value of a K-Na ion exchange layer formed by the strengthened aluminosilicate glass is small, the depth is shallow, the CS value of a shallow surface layer is low, the microhardness is poor, cracks are easily generated, and the falling resistance of corresponding products is reduced. When Na is present₂When the mass percentage of O is higher than 11%, the aluminosilicate glass has a poor network structure, the stability of mechanical properties and thermal properties is reduced, and the chemical durability is poor. Further, Na₂The mass percentage of O is 7-10%.

Potassium oxide (K)₂O) improves the melting properties of aluminosilicate glasses. K₂O and Li₂O and Na₂O can form mixed alkali effect, and can reduce the high-temperature viscosity of the aluminosilicate glass. K₂The mass percentage of O is 1-6%. When K is₂When the mass percentage of O is less than 1%, the stress depth of a K-Na ion exchange layer formed by the chemically strengthened aluminosilicate glass is shallow, which is not beneficial to the migration of K + ions to an inner layer in the ion exchange process. When K is₂When the content of O is more than 6% by mass, the network structure of the aluminosilicate glass is deteriorated, the stability of the thermal properties is lowered, and the weather resistance is deteriorated. Further, K₂The mass percentage of O is 2.5-4%.

Zirconium oxide (ZrO)₂) The chemical stability and the ion exchange performance of the aluminosilicate glass can be improved, the surface hardness of the aluminosilicate glass is increased, and the pressure required by the aluminosilicate glass to form cracks can be improved, so that the aluminosilicate glass is more scratch-resistant and more drop-resistant. Only a small amount of ZrO is required₂Can meet the requirements, and ZrO₂Too much will significantly increase the melting temperature of the aluminosilicate glass and cause defects such as stones. Therefore, in the present embodiment, ZrO₂The mass percentage of the component (A) is 0.1-4%. Further, ZrO₂The mass percentage of the component (A) is 0.1-4%.

In one embodiment, SiO is in the above aluminosilicate glass₂The mass percentage content of the active ingredients is 58-63 percent; and/or

Al in the above aluminosilicate glass₂O₃The mass percentage content of the compound is 16-24 percent; and/or

Li in the above aluminosilicate glass₂The mass percentage of O is 3-5.5%; and/or

Na in the above aluminosilicate glass₂The mass percentage of O is 7-10%; and/or

K in the above aluminosilicate glass₂The mass percentage of O is 2.5-4%; and/or

In the above aluminosilicate glass, B₂O₃The mass percentage content of the compound is 0.1-3 percent; and/or

ZrO in the above aluminosilicate glass₂The mass percentage of the component (A) is 0.1-4%.

Further, Al is contained in the above aluminosilicate glass₂O₃The mass percentage of the component (A) is 19-22%.

In one embodiment, the aluminosilicate glass further comprises MgO in an amount of not more than 4% by mass. Magnesium oxide (MgO) can reduce the viscosity of aluminosilicate glass at high temperature, promote the melting and clarification of the aluminosilicate glass, enhance the stability of the network space of the aluminosilicate glass at low temperature, and reduce the thermal expansion coefficient of the aluminosilicate glass to a certain extent, but MgO has the function of inhibiting the ion exchange of a chemical strengthening process. It should be noted that, high temperature in this context means a temperature above 1400 ℃; the glass is melted at a temperature above 1400 ℃. Low temperature in this context means a temperature below 800 ℃; the glass is convenient to be subjected to glass transition and annealing under the condition that the temperature is lower than 800 ℃. Therefore, the MgO content by mass is not more than 4%. When the mass percentage of MgO exceeds 4 percent, Mg²⁺The ion exchange capacity of the aluminosilicate glass is severely hindered, which in turn leads to a significant reduction in the depth of the surface compressive stress layer. Furthermore, the mass percentage of MgO is 1% -3%.

In one embodiment, the aluminosilicate glass comprises 55-65% of SiO by mass percentage₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂And not more than 4% MgO.

Further, the aluminosilicate glass comprises 58 to 63 percent of SiO₂16 to 24 percent of Al₂O₃3 to 5.5 percent of Li₂O, 7 to 10 percent of Na₂O, 2.5 to 4 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂And 1 to 3 percent of MgO.

In one embodiment, the aluminosilicate glass further comprises ZnO with the content not more than 3% by mass percentage. ZnO can enhance the network space stability of the aluminosilicate glass at low temperature, but ZnO also has obvious barrier effect on ion exchange. Therefore, the mass percentage of ZnO does not exceed 3 percent.

In one embodiment, the aluminosilicate glass comprises 55-65% of SiO by mass percentage₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂And no more than 3% ZnO.

In one embodiment, the aluminosilicate glass comprises 55-65% of SiO by mass percentage₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂No more than 4% MgO and no more than 3% ZnO. Further, the aluminosilicate glass comprises 58% -63% of SiO₂16 to 24 percent of Al₂O₃3 to 5.5 percent of Li₂O, 7 to 10 percent of Na₂O, 2.5 to 4 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂1 to 3 percent of MgO and less than or equal to 1.5 percent of ZnO.

In one embodiment, the aluminosilicate glass further comprises P with a content of not more than 3% by mass₂O₅. Generally in Al₂O₃When the content of (B) is lower, P is introduced₂O₅，P₂O₅Into the aluminosilicate glass network, making the network voids larger than the aluminotetrahedra, and thus significantly increasing the ion exchange capacity. More importantly, P₂O₅Can be introduced intoThe strain point of the glass is improved in one step, the problem of stress relaxation in the ion exchange process can be relieved to a certain extent, and the surface compressive stress value after strengthening is higher. However, too much P₂O₅The introduction leads to a significant increase in the coefficient of thermal expansion and, on the contrary, to a reduction in the value of the surface compressive stress. Thus, P₂O₅The mass percentage of (A) is not more than 3%. Further, P₂O₅The mass percentage of (A) is not more than 1%.

In one embodiment, the aluminosilicate glass comprises 55-65% of SiO by mass percentage₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂And not more than 3% of P₂O₅. Further, the aluminosilicate glass comprises 58% -63% of SiO₂16 to 24 percent of Al₂O₃3 to 5.5 percent of Li₂O, 7 to 10 percent of Na₂O, 2.5 to 4 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂And not more than 3% of P₂O₅。

In one embodiment, the aluminosilicate glass comprises 55-65% of SiO by mass percentage₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂Not more than 4% MgO and not more than 3% P₂O₅. Further, the aluminosilicate glass comprises 58% -63% of SiO₂16 to 24 percent of Al₂O₃3 to 5.5 percent of Li₂O, 7 to 10 percent of Na₂O, 2.5 to 4 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO_2、Not more than 3% of P₂O₅And 1 to 3 percent of MgO.

In one embodiment, the aluminosilicate glass comprises 55-65% of SiO by mass percentage₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂No more than 3% ZnO and no more than 3% P₂O₅. Further, the aluminosilicate glass comprises 58% -63% of SiO₂16 to 24 percent of Al₂O₃3 to 5.5 percent of Li₂O, 7 to 10 percent of Na₂O, 2.5 to 4 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂No more than 1.5% of ZnO and no more than 1% of P₂O₅。

In one embodiment, the aluminosilicate glass comprises 55-65% of SiO by mass percentage₂13 to 26 percent of Al₂O₃2 to 6 percent of Li₂O, 6 to 11 percent of Na₂O, 1 to 6 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂MgO not more than 4%, ZnO not more than 3% and P not more than 3%₂O₅. Further, the aluminosilicate glass comprises 58% -63% of SiO₂16 to 24 percent of Al₂O₃3 to 5.5 percent of Li₂O, 7 to 10 percent of Na₂O, 2.5 to 4 percent of K₂O, 0.1-3% of B₂O₃0.1 to 4 percent of ZrO₂1 to 3 percent of MgO, no more than 1.5 percent of ZnO and no more than 1 percent of P₂O₅。

In one embodiment, SiO is in the above aluminosilicate glass₂The mass percentage content of the active ingredients is 58-63 percent; and/or

Al in the above aluminosilicate glass₂O₃The mass percentage content of the compound is 16-24 percent; and/or

Li in the above aluminosilicate glass₂Mass percent of OThe amount is 3 to 5.5 percent; and/or

Na in the above aluminosilicate glass₂The mass percentage of O is 7-10%; and/or

K in the above aluminosilicate glass₂The mass percentage of O is 2.5-4%; and/or

In the above aluminosilicate glass, B₂O₃The mass percentage content of the compound is 0.1-3 percent; and/or

ZrO in the above aluminosilicate glass₂The mass percentage content of the compound is 0.1-4 percent; and/or

The mass percentage of MgO in the aluminosilicate glass is 1-3%; and/or

The mass percentage of ZnO in the aluminosilicate glass is not more than 1.5%; and/or

P in the above aluminosilicate glass₂O₅The mass percentage of (A) is not more than 1%.

An embodiment of the present invention further provides a method for manufacturing strengthened glass, including steps S110 to S160.

Step S110 is to prepare an aluminosilicate glass, wherein the aluminosilicate glass is the aluminosilicate glass according to any one of the above embodiments.

Specifically, the step of preparing the aluminosilicate glass comprises: mixing the raw materials for preparing the silicate glass with a glass clarifier, and then melting at 1600-1680 ℃ to obtain molten glass; then, the glass melt is molded and annealed at 550 to 650 ℃ to obtain the silicate glass.

Furthermore, the melting temperature is 1650-1680 ℃. The melting is carried out under the condition of 1650-1680 ℃, so that the glass can achieve a better clarification and homogenization effect. The annealing temperature is 600-650 ℃. Annealing at 600 c to 650 c allows the glass to relieve residual stresses in a shorter time.

In the present embodiment, the aluminosilicate glass is plate-shaped; the thickness of the aluminosilicate glass is 0.5 mm-2 mm; the aluminosilicate glass has a size of 4 inches to 20 inches. Of course, in other embodiments, the size and thickness of the aluminosilicate glass may be adjusted according to actual needs.

And step S120, polishing the aluminosilicate glass.

Specifically, the surface flatness of the aluminosilicate glass after polishing does not exceed 0.01 mm.

In this embodiment, the surface of the aluminosilicate glass is polished by using a disk brush in combination with cerium oxide polishing powder. Of course, the polishing is not limited to the use of a disc brush, other polishing tools commonly used in the industry can be used, and the polishing powder is not limited to cerium oxide, but also other polishing powders commonly used in the industry. It should be noted that if the surface of the aluminosilicate glass is flat and smooth and reaches a surface flatness of 0.01mm, for example, if the aluminosilicate glass is float glass, the surface does not need to be polished, and step S120 may be omitted.

Step S130, the aluminosilicate glass is subjected to a hot bending treatment.

In this embodiment, the flat aluminosilicate glass is formed into a curved glass by placing the aluminosilicate glass in a hot bending machine, and performing preheating, pressing, and cooling, thereby completing the hot bending process. Of course, the curved aluminosilicate glass may be obtained by treating the aluminosilicate glass in a manner commonly used in the art. Note that if it is not necessary to process the aluminosilicate glass into a curved glass, the hot bending process is not necessary, and step S130 may be omitted.

And step S140, cleaning the aluminosilicate glass.

In this embodiment, when the aluminosilicate glass is cleaned, deionized water is used in combination with a rolling brush for cleaning. Of course, in other embodiments, other cleaning agents such as ethanol and acetone can be used for cleaning, and the cleaning is not limited to the use of a rolling brush, and other tools can be used for cleaning. And (3) drying the aluminosilicate glass after cleaning. It should be noted that if the surface of the aluminosilicate glass is relatively clean, cleaning is not required, and step S140 may be omitted.

And S150, immersing the aluminosilicate glass into the molten salt for ion exchange to obtain the strengthened glass.

In particular, the molten salt comprises NaNO₃And KNO₃. Li of aluminosilicate glass during ion exchange⁺Na with molten salt⁺Exchange rate of (A) and Na of aluminosilicate glass⁺K with molten salts⁺The ratio of the exchange rates of (A) is 4.8 to 6.3. Further, Li of aluminosilicate glass⁺Na with molten salt⁺Exchange rate of (A) and Na of aluminosilicate glass⁺K with molten salts⁺The ratio of the exchange rates of (a) is 5.5 to 6.3.

In particular, the molten salt comprises NaNO₃And KNO₃. The ion exchange speed of the pure potassium nitrate molten salt and the glass is too high, so that a large amount of K is easily caused⁺In a short time into the glass, these K⁺And the ion exchange material is accumulated on the shallow surface layer of the glass, is not easy to further migrate inwards, and simultaneously blocks the channel for the entry of ions, so that the ion exchange cannot be carried out continuously. Therefore, the pure potassium nitrate molten salt is not easy to obtain good ion exchange effect. This embodiment controls KNO₃With NaNO₃The ratio of (A) to (B) to control the Li-Na ion exchange rate and the Na-K ion exchange rate.

Further, the molten salt comprises 5-25% of NaNO by mass percentage₃And 75 to 95 percent of KNO₃. When NaNO is present₃When the content of (b) is less than 5% by mass, the ion exchange rate of Li-Na is slow and K is liable to occur⁺Surface enrichment of (3) blocking ion exchange of Li-Na; when NaNO is present₃When the content of (b) is more than 25% by mass, the Na — K ion exchange efficiency is lowered, and a high surface compressive stress is likely not to be formed on the surface of the aluminosilicate glass. Further, the molten salt comprises 5% -10% of NaNO₃And 90% -95% KNO₃。

In the traditional two-step or multi-step ion exchange chemical strengthening process, pure KNO is generally adopted as molten salt₃Or KNO₃With NaNO₃But the concentration of the molten salts can deviate significantly after a period of use. With Na⁺The change in concentration is taken as a reference, Na⁺The concentration variation range is generally controlled within 6000ppm, more strictly controlled within 4000ppm, once Na in molten salt⁺If the concentration deviation exceeds this range, the strengthening performance cannot be ensured, resulting in a low process yield. Therefore, the molten salt needs to be replaced frequently in the actual preparation process to meet the processing yield, but the frequent replacement of the molten salt affects the production efficiency and increases the production cost. In the method for producing a strengthened glass according to the present embodiment, Na in the molten salt is caused to exist by using the above aluminosilicate glass and controlling the conditions for ion exchange⁺The concentration of (2%) can fluctuate within a range of 2%, and the range of fluctuation of the CS value in the reinforcement performance is within 2.5%, and the range of fluctuation of the DOL is within 1%. In other words, Na of the molten salt for ion exchange in the present embodiment⁺The change value of the concentration can be 20000ppm, the service life of the fused salt is greatly prolonged, the production efficiency and the processing yield are improved, and the production cost is reduced.

Specifically, the temperature of the ion exchange is 390 ℃ to 460 ℃. When the temperature of the ion exchange is below 390 ℃, the ion exchange rate is slower and increased strengthening time is required to obtain acceptable mechanical properties. When the temperature of ion exchange is higher than 460 ℃, stress relaxation is liable to occur to cause a decrease in CS. On the premise that the depth of the surface compressive stress layer meets the requirement, a larger CS value is difficult to obtain, and the problems of warping, self-exposure and the like which influence the yield rate are easily caused by high strengthening temperature. Further, the temperature of the ion exchange is 410 ℃ to 440 ℃.

Specifically, the time of ion exchange is 180 min-300 min. Due to the adjustment of the ion exchange speed, when the ion exchange time is less than 180min, the ion exchange degree is insufficient, and the CS and DOL values cannot reach the expectation. When the time of ion exchange is longer than 300min, the method has no strong promotion effect on CS promotion, and has no great practical significance on DOL value increase, and the production cost is increased. Further, the time of ion exchange is 210 min-270 min.

In one embodiment, the molten salt comprises 5% to 25% NaNO₃And 75 to 95 percent of KNO₃The temperature of ion exchange is 390-460 ℃, and the time of ion exchange is 180-300 min. The molten salt comprises 5 to 25 percent of NaNO₃And 75 to 95 percent of KNO₃Ion exchange temperature of 390Under the conditions of temperature of 460 ℃ and ion exchange time of 180 min-300 min, the ion exchange depth of the aluminosilicate glass is not less than 75 μm, and the surface compressive stress value is 650-900 MPa. Further, the molten salt comprises 5% -10% of NaNO₃And 90% -95% KNO₃The temperature of ion exchange is 410-440 ℃, and the time of ion exchange is 210-270 min.

And step S160, removing the molten salt on the surface of the strengthened glass.

Specifically, the tempered glass is taken out of the molten salt and placed in a preheating furnace at the temperature of 390-460 ℃, the power supply of the preheating furnace is turned off, and the tempered glass is placed in water for ultrasonic cleaning after being cooled to the room temperature along with the furnace so as to remove the residual molten salt on the surface of the tempered glass. In the present embodiment, the time for ultrasonic cleaning is 0.5 to 1 hour. Further, the water temperature of ultrasonic cleaning is 16-100 ℃.

The preparation method of the tempered glass at least has the following advantages:

(1) the tempered glass prepared by the preparation method of the tempered glass has more excellent performance of resisting rough ground falling and breaking: according to the preparation method of the tempered glass, Li-Na ion exchange and Na-K ion exchange simultaneously occur, and the ratio of the exchange rate of the Li-Na ion exchange to the exchange rate of the Na-K ion exchange is controlled to be 4.8-6.3, so that the surface compression stress layer formed by the aluminosilicate glass is a composite compression stress layer, and the composite compression stress layer comprises a Na-K ion exchange layer close to the surface of the glass and a Li-Na ion exchange layer close to the inner layer of the glass. The depth of the surface compressive stress layer of the tempered glass prepared by the preparation method of the tempered glass is not less than 75 mu m, and the surface compressive stress value is not less than 650 MPa. Therefore, the tempered glass prepared by the preparation method of the tempered glass has more excellent performance of resisting rough ground falling and breaking and higher falling resistance.

(2) The strengthened glass prepared by the preparation method of the strengthened glass has better mechanical impact resistance: the glass is easy to self-explode when the intermediate tensile stress value formed in the glass is more than 110MPa, and particularly the thickness of the glass is less than 0.5 mm. In the traditional chemical strengthening process, the intermediate tensile stress value formed in the glass is generally greater than 110MPa, so that spontaneous explosion is easy to occur, and the crack propagation of the microcracks on the surface of the glass is easy to induce due to the large intermediate tensile stress value in the glass. Therefore, when the glass is impacted by external force, the glass strengthened by the traditional chemical strengthening process is more easily broken, and the falling breakage resistance of rough ground is obviously lower. The intermediate tensile stress of the tempered glass with the thickness of 0.5mm prepared by the method for preparing the tempered glass is not higher than 80MPa, and the intermediate tensile stress of the tempered glass with the thickness of 0.7mm is not higher than 60 MPa. Therefore, compared with the traditional chemical strengthening process, the strengthened glass prepared by the preparation method of the strengthened glass has better mechanical impact resistance and higher falling resistance.

(3) The preparation method of the strengthened glass has shorter period for preparing the strengthened glass: when the high-alumina glass with the surface compressive stress layer depth of more than 60 mu m is prepared by adopting the traditional one-step ion exchange chemical strengthening process, the ion exchange time needs more than 420min, and the stress layer depth of the strengthened glass prepared by the traditional one-step ion exchange chemical strengthening process is difficult to reach 80 mu m. When the two-step or multi-step ion exchange chemical strengthening process is adopted, although the strengthened glass with the surface compressive stress layer depth of more than 80 μm and the surface compressive stress value of more than 600MPa can be prepared, the two-step or multi-step ion exchange chemical strengthening process is difficult to control the ion exchange time within 300 min. The preparation method of the strengthened glass can control the ion exchange time to be 300min, and the depth of the surface compressive stress layer of the strengthened glass prepared by the preparation method of the strengthened glass is not less than 75 mu m, and the surface compressive stress value is not less than 650 MPa.

(4) The preparation method of the strengthened glass has lower requirement on the precision of the molten salt: in the conventional chemical strengthening process, the concentration of the molten salt can deviate obviously after the molten salt is used for a period of time. With Na⁺The change in concentration of (A) is exemplified by Na⁺The concentration of (A) is controlled within 6000ppm in general, and within 4000ppm more strictly, once Na in molten salt⁺The deviation value of the concentration exceeds this range,the reinforcement performance cannot be guaranteed. Therefore, conventional chemical strengthening processes require frequent replacement of the molten salt to meet process yield. The preparation method of the strengthened glass adopts the aluminosilicate glass and controls the ion exchange conditions to ensure that Na of molten salt⁺The variation range of the concentration of (2) is within 20000ppm, the service life of the fused salt is greatly prolonged, the production efficiency and the processing yield are improved, and the production cost is reduced.

The invention also provides the tempered glass prepared by the preparation method of the tempered glass. The depth of the surface compressive stress layer of the tempered glass is not less than 75 μm, and the surface compressive stress value is not less than 650 MPa. When the thickness of the strengthened glass is 0.5mm, the intermediate tensile stress of the strengthened glass is not higher than 80 MPa; when the thickness of the tempered glass is 0.7mm, the intermediate tensile stress of the tempered glass is not higher than 60 MPa. The strengthened glass has excellent rough ground falling and breaking resistance, mechanical impact resistance and good falling resistance.

The embodiment of the invention also provides application of the tempered glass in preparing a cover plate or a back plate. In addition, the invention also provides an application of the tempered glass in preparing a device containing the tempered glass.

An embodiment of the present invention also provides an apparatus comprising the above strengthened glass.

In this embodiment, the device is an electronic device, such as a mobile phone or a tablet computer.

Specifically, the device comprises a cover plate, and the cover plate comprises the tempered glass. Further, the cover plate is processed from the tempered glass.

In one embodiment, the device comprises a back plate comprising the tempered glass. Further, the back plate is processed from the tempered glass.

In one embodiment, the device comprises a cover plate and a back plate, wherein the cover plate comprises the tempered glass, and the back plate comprises the tempered glass.

Of course, in other embodiments, the device is a non-electronic device that includes the strengthened glass described above.

The device has good anti-falling performance due to the tempered glass.